TWI662149B - Methods and apparatuses for showerhead backside parasitic plasma suppression in a secondary purge enabled ald system - Google Patents

Abstract

The method disclosed herein is a method of depositing a thin film of material on a semiconductor substrate, and the method uses a secondary cleaning. The methods include flowing a thin film precursor into a processing chamber, and causing the thin film precursor to be adsorbed on a substrate in the processing chamber, so that the precursor forms an adsorption limiting layer on the substrate. The method further includes cleaning the processing chamber by using a primary purge gas, removing at least some unadsorbed film precursors from a volume around the adsorbed precursors, and then, using a secondary purge gas. While flowing into the processing chamber, the adsorbed thin film precursor is caused to react, resulting in the formation of a thin film layer on the substrate. The secondary cleaning gas includes chemical species having a free energy and / or a dissociation energy equal to or greater than O ₂ . Also disclosed herein is a device for implementing the above method.

Description

Method and equipment for suppressing parasitic plasma on back side of shower head in atomic layer deposition system started by secondary cleaning

The invention relates to a method and equipment for suppressing parasitic plasma on the back side of a shower head in an atomic layer deposition system started by secondary cleaning.

As the size of devices and features in the semiconductor industry continues to miniaturize, and as 3D device structures (such as Intel's tri-gate transistor structures) become more prevalent in integrated circuit (IC) designs, thin layers of semiconductors The ability to form a thin film (a thin film of material with a uniform thickness relative to the shape of the underlying structure, even if the underlying structure is not flat) will continue to increase in importance. Atomic layer deposition (ALD) is a thin film formation technology suitable for depositing conformal thin films. This is because a single cycle of ALD only deposits a single thin layer of material, and its thickness is subject to adsorption before the chemical reaction itself forming the thin film The amount of one or more thin film precursor reactants on the surface of the substrate (ie, forming an adsorption limiting layer) is limited. Multiple "ALD cycles" can then be applied to accumulate films of the desired thickness, and because each layer is thin and conformal, the final film substantially conforms to the shape of the underlying device structure.

However, there are many challenges related to ALD processing. These challenges are often related to the fact that because a single cycle of ALD only deposits a thin adsorption-limiting layer, many ALD cycles are required to accumulate thin films with an apparent thickness. Each cycle takes time and requires sequential operation of the repeating equipment (for completing the deposition process). Therefore, I seek improved methods and equipment to increase wafer processing speed and also improve the life and maintenance requirements of substrate processing hardware (for performing ALD operations).

The method disclosed herein is a method of depositing a thin film of material on a semiconductor substrate, and the method uses a secondary cleaning. The methods include flowing a thin film precursor into a processing chamber, and causing the thin film precursor to be adsorbed on a substrate in the processing chamber, so that the precursor forms an adsorption limiting layer on the substrate. The method further includes cleaning the processing chamber by using a primary purge gas, removing at least some unadsorbed film precursors from a volume around the adsorbed precursors, and then, using a secondary purge gas. While flowing into the processing chamber, the adsorbed thin film precursor is caused to react, resulting in the formation of a thin film layer on the substrate. The secondary cleaning gas includes chemical species having a free energy and / or a dissociation energy equal to or greater than O ₂ .

Also disclosed herein is a device for depositing a thin film of a material on a semiconductor substrate. The equipment includes a processing chamber, a substrate holder located in the processing chamber, a shower head (for allowing a thin film precursor and a cleaning gas to flow into the processing chamber), a shower head shaft Sleeve (for the secondary cleaning gas to flow into the processing chamber), one or more primary flow valves (for controlling the flow rate of the film precursor and the primary cleaning gas flow through the showerhead), one Or more secondary flow valves (for controlling the flow of secondary purge gas through the sprinkler sleeve), a valve-operated vacuum source (for removing primary and secondary purge gas from the Removed from the processing chamber and the film precursor from the surrounding volume of the substrate in the processing chamber), a plasma generator (for generating the plasma in the processing chamber), and including a machine One or more controllers with readable instructions (for operating one or more valves, vacuum sources, and plasma generators, depositing a thin film of material on a semiconductor substrate). The instructions of the controller may include: instructions for operating the primary flow valve to flow the film precursor into the processing chamber; and controlling conditions in the processing chamber such that the film precursor is adsorbed on the process Instructions for forming an adsorption limiting layer on the substrate in the chamber; for operating the primary flow valve to flow primary cleaning gas into the processing chamber; and for operating the valve to drive a vacuum source to clean the primary Instruction for gas evacuation (by which at least some unadsorbed thin film precursors are removed from the surrounding volume of the adsorbed precursors); for operating the plasma generator to form in the processing chamber A plasma instruction that activates the reaction of the adsorbed thin film precursor to form a thin film layer on the substrate; and is used to operate while activating the reaction of the adsorbed thin film precursor through the plasma The secondary flow valve is an instruction to flow a secondary purge gas (including O ₂ ) into the processing chamber.

In order to provide a comprehensive understanding of the invention, many specific details are set forth in the following embodiments. The invention may, however, be practiced without some or all of these specific details. In some instances, well-known process operations have not been described in detail in order to unnecessarily obscure the present invention. Although the present invention is described in conjunction with specific detailed embodiments, it should be understood that these specific detailed embodiments are not intended to limit the scope of the inventive concepts disclosed herein.

The method and equipment disclosed herein are used to suppress the generation of parasitic plasma in a semiconductor substrate processing chamber, and the semiconductor substrate processing chamber is used to deposit a conformal film through atomic layer deposition (ALD).

ALD is used to deposit a thin film of material with a desired thickness by performing a plurality of "ALD cycles", and each cycle deposits only a thin layer of material (usually only one molecular layer). As will be described in detail below, a basic ALD cycle for depositing a single material layer on a substrate in a processing chamber includes: (i) adsorbing a thin film precursor on the substrate such that it forms an adsorption limiting layer, (ii) removing (at least a few) unadsorbed film precursors from the volume surrounding the adsorbed precursors, and (iii) removing the unadsorbed precursors, causing the adsorbed film precursors to As a result, a thin film layer is formed on the substrate. Generally, the ALD cycle further includes operation (iv) to remove the desorbed thin film precursor and / or reaction byproducts from the surrounding volume of the thin film layer (formed on the substrate).

Removal in operations (ii) and (iv) can be achieved by purge the surrounding volume of the substrate, evacuation by pumping to base pressure (pump-to-base), and the like. In some embodiments, the cleaning may be logically divided into "primary cleaning" or "burst cleaning" and "secondary cleaning" as referred to herein. The one purge involves the use of a "purge purge gas" referred to herein, which is derived from the "purge purge gas source" and is introduced into the processing chamber via a purge purge gas flow path (through one or more purge purge gas inlets) Room. Similarly, this secondary purge involves the use of what is referred to herein as a "secondary purge gas" that originates from a "secondary purge gas source" and passes through a secondary purge gas flow path (through one or more secondary purges) Gas inlet) into the processing chamber.

The one cleaning occurs during operation (ii), and in the embodiment where there is another cleaning in operation (iv), the one cleaning also occurs during the other cleaning. However, this one purge usually does not occur during operations (i) and (iii), and in some embodiments, substantially all of the purge gas has been removed from the processing chamber before the reaction of operation (iii). except. Therefore, because the flow of the primary purge gas is intermittent, the primary purge is also referred to herein as a "burst purge" (using a "burst purge gas"). The terms washing once and washing suddenly are used synonymously herein.

The term “secondary cleaning” is considered to be different from “primary cleaning” in this article. In contrast to this primary cleaning, during the secondary cleaning, the gas flows into the process during the reaction (which occurs in operation (iii)) in a manner that does not substantially interrupt or interfere with the reaction process (which occurs on the substrate surface). In the chamber. In some embodiments, the secondary purge gas also flows into the processing chamber during operations (i)-(ii) and / or (iv), and in some such embodiments, throughout the operation (i )-(iv), it continuously flows into the processing chamber.

The flow rate of the secondary cleaning gas flowing into the processing chamber may be different from the flow rate of the primary cleaning gas flowing into the processing chamber, depending on the embodiment. In some embodiments, the primary purge gas is flowed into the processing chamber at a rate of about 1,000 to 100,000 seem, or preferably about 5,000 to 45,000 seem, or even about 10,000 to 30,000 seem. In some embodiments, the secondary purge gas flows into the processing chamber at a rate of about 1 to 50,000 seem, or preferably about 1 to 30,000 seem, or even about 1,000 to 20,000 seem.

The use of secondary cleaning in an ALD process can yield several beneficial effects, related to the secondary cleaning being initiated during operation (iii), and the secondary cleaning gas being directed to the distal region of the processing chamber (rather than (Directed directly to the substrate like a single cleaning). The flow of the secondary cleaning gas to the distal region of the chamber (that is, the region that is not directly close to the substrate surface) can first help remove excess unadsorbed thin film precursors from the processing chamber. Furthermore, even Helps prevent film precursors from flowing to such distal regions in the chamber. In order to achieve the latter effect, the secondary cleaning is also initiated during operation (i) (when the film precursor flows into the chamber). Applying a secondary cleaning during operation (iii) can protect the inside surface of the chamber, for example, from any parasitic deposition. Parasitic deposition may occur for the following reasons: During the reaction process (which occurs on the substrate surface), the precursor The surface is desorbed and then re-adsorbed and reacted elsewhere, such as on the side wall of the chamber. Before describing a detailed example of a substrate processing apparatus equipped to apply secondary cleaning, an overall overview of a thin film deposition apparatus is now provided. [Outline of thin film deposition equipment]

The operation of depositing a thin film on a semiconductor substrate can be roughly performed in a substrate processing apparatus as shown in FIG. 1. The apparatus 100 (described in further detail below) of FIG. 1 has a single processing chamber 102 and a single substrate holder 108 in an internal volume maintained under vacuum through a vacuum pump 118. A gas delivery system that is fluidly coupled to the processing chamber 102 for the transport of, for example, film precursors, carrier gases, and / or cleaning and / or processing gases, secondary reactants, etc. 101 与 喷头 106. An apparatus for generating a plasma in a processing chamber is also presented in Figure 1 (to be described in further detail below). In summary, the apparatus schematically depicted in FIG. 1 provides a basic apparatus (as detailed below) that performs a thin film deposition operation (such as ALD) on a semiconductor substrate.

Although in some cases, a substrate processing apparatus as shown in FIG. 1 is sufficient, when a time-consuming thin film deposition operation is involved, substrate processing throughput is improved by performing a plurality of deposition operations in parallel on a plurality of semiconductor substrates at the same time. The output is advantageous. For this purpose, multi-station substrate processing equipment may be applied, as schematically depicted in FIG. 2. The substrate processing apparatus 200 of FIG. 2 still uses a single substrate processing chamber 214, however, there are a plurality of substrate processing stations in a single internal volume defined by the cavity wall of the processing chamber, and each substrate processing station is available A processing operation is performed on a substrate held on a wafer holder in the processing station. In this specific embodiment, the multi-station substrate processing apparatus 200 is shown as having four processing stations 201, 202, 203, and 204. The apparatus also employs a substrate loading device (in this example, a substrate handling machine 226) for loading substrates into processing stations 201 and 202; and a substrate transfer device (in this example, a substrate rotation rack 290). ) For transferring substrates between a plurality of processing stations 201, 202, 203, and 204. Other similar multi-station substrate processing equipment may have more or fewer processing stations, depending on the embodiment and, for example, the desired level, size / space constraints, etc. of parallel wafer processing. A controller 250 is also shown in FIG. 2 (which will be described in further detail below), which also helps achieve the goal of performing an efficient substrate deposition operation (introducing primary and secondary cleaning gases in an atomic layer deposition (ALD) operation).

It should be noted that, in terms of both equipment cost and operability cost, various effects can be achieved by using the multi-station processing equipment shown in FIG. 2. For example, in terms of all four processing stations, a single vacuum pump (not shown in Figure 2 but such as vacuum pump 118 in Figure 1) can be used to establish a single high vacuum environment for all four processing stations and is available It can be used to evacuate the failed process gas. Depending on the embodiment, each processing station may have its own dedicated shower head (for example, see the shower head 106 in FIG. 1) for gas transportation, but share the same gas transmission system (for example, the gas transportation in FIG. 1). System 101). Similarly, some components of the plasma generator equipment (such as a power supply) can be shared in the processing station, but some aspects can be processed by a specific station (such as the use of sprinklers for the application of plasma generating equipment). Potential-see discussion in Figure 1 below), depending on the embodiment. However, it should be known once again that this effect can be achieved by using more or fewer processing stations in each processing chamber (e.g., each processing chamber has 2, 3, 5, 6, 7, 8 , 9, 10, 11, 12, 13, 14, 15, or 16, or more processing stations) to a greater or lesser extent. [Implementation and application of secondary cleaning]

Substrate processing equipment designed with shower heads especially benefits from the use of secondary cleaning. In this design, the main purpose of the showerhead is to provide a mechanism by which the thin film precursor is introduced into the processing chamber (for substrate surface adsorption in operation (i)). Compared to what can be achieved with only a few nozzles as the point source for the flow rate, the shower head design allows the film precursor flow rate to be more evenly distributed on the substrate surface. Once the appropriate potential is applied, the showerhead can also be used as one of the two electrodes (for the plasma generation in operation (iii), which causes activation of the surface reaction). In addition to these uses, the shower head can also be used to introduce the flow of the primary cleaning gas into the processing chamber during operation (ii) and / or (iv), so that a better cleaning gas can be achieved Spatial uniformity. However, for the method for introducing the cleaning gas into the processing chamber, a subsequent problem is that the flow generally cannot effectively clean the cavity located on the back side of the shower head. Therefore, it is very beneficial to make the secondary cleaning gas flow directly into the space / cavity on the backside / overhead of the showerhead, because this can minimize or avoid the backside of the showerhead and Undesirable deposition of lateral / upper cavity walls etc.

Such an embodiment is schematically illustrated in FIG. 3. FIG. 3 shows a schematic cross-sectional view of a single-station substrate processing equipment 300, which has a processing chamber 102, a shower head 106, and a shower head sleeve 330, and draws the flow paths 310 and 320 of the primary and secondary cleaning gases, respectively. . In the configuration shown in FIG. 3, the primary cleaning gas from the primary cleaning gas source 312 flows into the chamber 102 through the shower head 106, but the secondary cleaning gas from the secondary cleaning gas source 322 is transmitted through the spray The shower sleeve 330 flows into the chamber 102. Therefore, the secondary cleaning gas in this article is introduced into the processing chamber 102 near the central axis on the back side of the shower head 106 and has a flow rate substantially parallel to the plane of the substrate 112 (held on the support 108) To introduce. Before leaving the chamber near the cross plate 303, the secondary cleaning gas thus introduced will also flow around the sprinkler head and down the side wall of the chamber (as schematically depicted by arrows in the figure) Like). In this manner, the secondary purge gas can minimize and / or avoid deposition on the internal cavity walls of the cavity 102. In some examples, in the cavity on the back side of the shower head, the flow rate of the cleaning gas meets the Peclet condition (typically, the number of columns is greater than 1), so the reverse of the precursors in the cavity is avoided. Diffusion (or flow), which therefore reduces the effective chamber volume, but minimizes undesirable deposition effects.

An additional benefit of using this secondary purge gas (generally implemented in accordance with Figure 3) is the ability to use an inert gas (rather than a relatively expensive film precursor) to establish chamber pressure in the processing chamber. The higher chamber pressure can serve as a gas curtain for the film precursor, thereby increasing the partial pressure of the precursor in the substrate area, but reducing the partial pressure of the precursor elsewhere. Higher chamber pressure itself due to the higher pressure regime also inhibits parasitic deposition on the inside chamber surface / chamber wall, and also reduces the chance (or intensity) of parasitic plasma generation (below) Discussed in more detail).

Appropriate sprinklers and sprinkler bushings (similar to those schematically depicted in FIG. 3) that can be applied to generate primary and secondary purge gas flows will be described in further detail below with reference to FIGS. 6-9. The use of such secondary cleaning gas, the introduction of secondary cleaning gas on the back side of the shower head, and details of related equipment are also recorded in the previous US Patent Application No. 13/659231, with an application date of 2012 On October 24th, the case was named "SUPPRESSION OF PARASITIC DEPOSITION IN A SUBSTRATE PROCESSING SYSTEM BY SUPPRESSING PRECURSOR FLOW AND PLASMA OUTSIDE OF SUBSTRATE REGION". Its US Patent Publication No. 2013/0344245 is based on the full text and its various uses. Add references to this case. [Method and device for parasitic plasma suppression in secondary cleaning]

Because the secondary cleaning is typically performed during the ALD-treated film formation reaction operation (operation (iii) above), an inert gas is generally selected as the secondary cleaning gas so that it does not interfere with the film formation reaction. In the previous results, N _{2 was} usually selected as the secondary cleaning gas. However, in some applications (such as double-patterning), the nitrogen content of the deposited film must be strictly controlled, and the use of N ₂ as a secondary cleaning gas often results in nitrogen incorporation into the film. In deposited films, N ₂ is usually not a good choice.

This is illustrated in Table 1 below, which shows the composition of the 4 films that use a primary / burst purge ("BP") gas, a secondary purge ("2 ^nd P") gas, and a carrier 4 different combinations of gas to deposit. The silicon and oxygen contents are listed in raw ion counts; the nitrogen, hydrogen, and carbon contents are listed in density (counts / cm ³ ). Thin-film composition was measured using a secondary ion mass spectrometer (SIMS). The first line of the table shows the reference film composition. The film was prepared using N ₂ as a primary purge gas, a secondary purge gas, and a carrier gas. Relative to this reference composition, the second line of the table shows that replacing N ₂ as a primary / burst and secondary cleaning gas with Ar reduces the nitrogen concentration in the deposited film by about 40% Scale). Then, the example listed in the third row of the table illustrates that while maintaining N ₂ as the secondary purge gas, replacing Ar as the primary / burst purge gas did not produce a similar reduction in nitrogen concentration. Because Ar was used only once / burst cleaning and did not achieve the same reduction in nitrogen concentration, it can be inferred that the choice of once / burst cleaning gas has no significant effect on the nitrogen concentration in the deposited film. This can be reasonably explained based on the fact that during the film formation reaction step (operation (iii) above), there is no (or very little) once / burst cleaning gas present and may be incorporated into the deposit In the film. On the other hand, a secondary purge gas is typically present during the film formation reaction step (operation (iii)), so it will contribute chemical species to the deposited film. The last row in Table I (as another verification of this analysis) table lists the film composition using Ar as both the primary / burst purge gas and the carrier gas. Because this did not lead to a decrease in the nitrogen content (relative to the reference component), the following analysis results were verified: The main nitrogen contributor to the deposited film was a secondary purge gas. Table I : SIMS data of components measured from wafers under various cleaning conditions

Therefore, the above-mentioned SIMS experiment demonstrates that using argon (Ar) instead of N ₂ as an inert secondary cleaning gas in the ALD process is effective for controlling / reducing the nitrogen content in the final deposited film. However, experiments using argon have shown that argon is also not ideal as a secondary purge gas (although the reason is different from N ₂ ). Because the film formation reaction in operation (iii) is typically activated by plasma, in the processing chamber during the secondary cleaning, the RF electric field that generates the plasma generally exists. Experiments show that in addition to generating a "primary plasma" around the substrate surface (a plasma used to activate the surface reaction of the adsorbed thin film precursors), this RF electric field is also generated in the distal region of the chamber "Parasite Plasma". For example, in the embodiment (where the shower head is used to distribute both the film precursor and the primary cleaning gas, and where the secondary cleaning gas system is distributed from above / backside of the shower head) (as shown in the embodiment shown in FIG. 3) It was found that strong / dense parasitic plasma was generated in the area on the backside / upper side of the shower head of the processing chamber. Because this unexpected plasma was observed to be very bright, it is presumed to be very dense / strong. Furthermore, because the volume between the area above the showerhead and the top cavity wall / plate of the processing chamber is quite large, the volume of this plasma is quite large, coupled with its high plasma density It may attract a large amount of power to leave the main plasma (for activating the film formation reaction on the substrate).

The formation of parasitic plasmas is unpleasant for a variety of reasons: Parasitic plasmas are "uncontrolled" power sinks that may attract power away from the main plasma and reduce the density of the main plasma. In addition, because the density and power attraction of the parasitic plasma will change based on various factors, the impact of the parasitic plasma on the main plasma (active film formation reaction) will also change and cannot be predicted, which will then contribute to the wafer and wafer A major factor in the variation between. In addition, parasitic plasma causes enhanced deposition to occur on the cavity wall surface; this deposition may become a source of particles and contaminate the deposited film on the substrate. Therefore, the operation of strong / dense parasitic plasma occurs, causing long-term problems (reproducibility between wafers, tool drift, process particle performance, spraying) Head element and / or other chamber elements have increased erosion) and / or other yield issues, therefore, in order to avoid / minimize these undesirable results, an important goal is to partially or completely suppress / eliminate ALD Parasitic plasma generation in the processing system.

One method to solve this problem is to carefully choose a secondary cleaning gas, which does not easily form a strong plasma (or does not form a plasma at all) but still does not interfere with the film formation reaction (in operation (iii)) or adversely changes the composition of the film . One such option is the oxygen molecule (O ₂ ). When using O ₂ as the secondary cleaning gas and Ar as the primary cleaning gas, it was found that the parasitic plasma generated on the back side of the shower head was more than that generated when Ar was used as both the primary and secondary cleaning gas. Weak ground.

Without being limited to a specific theory, it is generally believed that the reason for the relatively weak (relative to Ar) of the parasitic plasma when using O ₂ is that compared to Ar-based plasmas, more RF power levels are required to maintain O ₂ -based electrical Pulp. It is conceivable that this is due to the huge dissociation energy related to the bonding of oxygen molecules and the high free energy related to the oxygen atoms. Therefore, it has been found that for a given RF power for maintenance, O ₂ -based plasmas have a low electron density (compared to other types of plasmas, such as Ar-based plasmas), so O ₂ The base plasma is called "weak plasma". In this way, in the plasma activation step of the ALD cycle, the RF power and sprinkler voltage used to generate / ignite the Ar plasma (between the sprinkler and the substrate) are insufficient to generate / ignite O ₂ The plasma (located in the cavity above the showerhead) or, if there is some ignition, the O ₂ plasma will be very weak (and apparently dim). Regarding other characteristics of the preferred secondary cleaning gas, it should be noted that, unlike N ₂ , not only was it found that the Ar / O ₂ mixture was compatible with the general plasma-activated ALD surface reaction, but also found that the presence of O ₂ did improve the film Quality (at least in some embodiments).

Numerous numerical and experimental studies have been completed to elaborate and quantify the following for specific examples: the extent to which RF power is drawn away from the main plasma due to the presence of Ar-based parasitic plasmas; and the use of O ₂ as a secondary The degree of improvement that can be achieved with a secondary purge gas.

Figure 2 lists five different sets of process conditions. These process conditions consist of primary / burst and secondary purge gas, and various combinations of RF power levels. A wafer is processed according to the five sets of process conditions listed in each table. The data shown in the graph from left to right are: RF power level (watts), average deposited film thickness (Å) (measured at 49 points on each wafer surface), NU% (percent of thickness unevenness) (Also measured 49 points on the surface of each wafer, 1 standard deviation, after scaling), the thickness range of the deposited film (the difference between the thinnest and thickest points of the deposited film), NU% (R / 2) (a statistical measure-called "half range nonuniformity"-defined as ½ * ( max _thickness - min _thickness ) / mean _thickness * 100%), each treatment Number of deposition cycles (using 4 processing stations), deposition rate per ALD cycle (e.g. 1.508 Å / cycle = 349.8 Å / (58 cycles x 4)), estimated power delivery (relative to using N ₂ / N ₂ (primary / secondary) cleaning combination), and power loss percentage (also relative to using N ₂ / N ₂ ). Figure II : Estimated main plasma power loss ( caused by parasitic plasma )

The strategy implemented in Figure II is to confirm the quantitative relationship between the deposition rate and the RF power level (in the absence of parasitic plasma), and then use Ar and O ₂ as the secondary cleaning gas to measure the deposition again Rate to estimate the degree of power loss in the presence of parasitic plasma. Therefore, the experiments corresponding to the first three rows in Figure II are: using N ₂ as both the primary and secondary cleaning gas, but the RF power levels in these three rows are different. This 3 rows of data points are then plotted in Figure 4 (deposition rate ("DepR") vs. RF power level), and the calculated best fit line is shown in the figure to show the difference between the deposition rate and power Relationship.

Next, the fourth line in Chart II shows the results of the deposition experiment (using Ar as both the primary / burst cleaning and the secondary cleaning gas). The graph shows an increase in the deposition rate of 1600 W from 1.508 Å / cycle (at an RF power of 1600 W and using N ₂ ) to 1.66 Å / cycle. From the relationship in FIG. 4 may be used to estimate the power loss with respect to N ₂ is approximately 47% (the deposition rate is inversely proportional to the power level; see Figure 4).

Finally, the fifth line in Chart II shows the effect of using O ₂ instead of Ar as the secondary purge gas. The graph shows that the deposition rate of 1600 W in this experiment dropped back to 1.545 Å / cycle, which is closer to the deposition rate when N ₂ was used. The corresponding power loss relative to N ₂ (because of the presence of parasitic plasma) is only 11%, which is a significant improvement compared to the use of Ar.

Therefore, the use of oxygen molecules has been found to substantially alleviate the problems discussed above. In short, these data and related calculations show that the RF power consumed by the parasitic plasma is close to 50% of the total RF power delivered to the processing station, however the replacement of O ₂ can reduce the power loss to nearly 10% (At least in this example). Summarizing the foregoing analysis, it can be concluded that the chemical species with large free energy and dissociation energy (relative to the free energy of argon-or other species of plasma used to help activate the reaction in operation (iii)) ), Is a good choice as a secondary cleaning gas. Of course, the presence / use of such chemical species must also be compatible with the film formation reaction and the desired characteristics of the deposited film (for the case of O ₂ but not for N ₂ ). Figure III unifies the key points above: [Atomic Layer Deposition Technology and the Embodiment of the Deposited Thin Film]

As mentioned earlier, as device sizes continue to miniaturize, and ICs are moving towards 3-D transistor and other 3-D structure applications, depositing precise amounts (thickness) of conformal thin film materials (especially dielectrics, But the ability to include a variety of dopant-containing materials has become even more important. Atomic layer deposition is a technique for achieving conformal thin film deposition, which typically involves multiple cycles of deposition to obtain a thin film of a desired thickness.

In contrast to chemical vapor deposition (CVD) processes, which use an activated gas phase reaction to deposit thin films, ALD processes use surface-mediated deposition reactions to deposit thin films layer by layer. For example, in one type of ALD processing, a first thin film precursor (P1) is introduced into a processing chamber in a gas form, is exposed to a substrate, and is then adsorbed on the surface of the substrate (generally aggregated) (population at the surface activation site). Some molecules of P1 (including the chemisorption species and the physisorption molecules of P1) form a condensed state on top of the surface of the substrate. The surrounding volume of the substrate surface is then evacuated to remove the gaseous and physically adsorbed P1 so that only chemisorbed species are left. A second thin film precursor (P2) is then introduced into the processing chamber, so that some molecules of P2 are adsorbed on the surface of the substrate. The surrounding volume of the substrate (in the processing chamber) was evacuated again, this time to remove unbound P2. Successively, the energy (such as heat or plasma energy) provided to the substrate activates the surface reaction between the adsorbed molecules of P1 and P2 to form a thin film layer. Finally, the surrounding volume of the substrate is evacuated again to remove unreacted P1 and / or P2, and / or reaction by-products (if present), ending a single cycle of ALD.

The ALD technology used to deposit conformal thin films (with a variety of chemicals), and many variations based on basic ALD processing, are described in detail in US Patent Application No. 13/084399, filed on 4/11/2011, as the case name "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION" (Attorney's case number NOVLP405); US Patent Application No. 13/242084, filing date is 9/23/2011, and the case name is "PLASMA ACTIVATED CONFORMAL DIELECTRIC FILM DEPOSITION", which is now the United States Patent Case No. 8637411 (Attorney's Case No. NOVLP427); U.S. Patent Application No. 13/224240, with filing date of 9/1/2011, named "PLASMA ACTIVATED CONFORMAL DIELECTRIC FILM DEPOSITION" (Agent Case No. ; And U.S. Patent Application No. 13/607386, filed on 9/7/2012, entitled "CONFORMAL DOPING VIA PLASMA ACTIVATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION" (Attorney's case number NOVLP488). The full text and its various uses are incorporated in this case. As described in these previous applications, the basic ALD cycle for depositing a single material layer on a substrate includes: (i) adsorbing a thin film precursor on the substrate such that it forms an adsorption limiting layer, (ii) ) Removing the unadsorbed precursor from the surrounding volume of the adsorbed precursor, (iii) reacting the adsorbed precursor to form a thin film layer on the substrate, and (iv) desorbing The thin film precursors and / or reaction byproducts are removed from the surrounding volume of the thin film layer (formed on the substrate). Removal in operations (ii) and (iv) can be achieved by cleaning, evacuating, and pumping the surrounding volume of the substrate to the base pressure. It should be noted that the basic ALD sequence of operations (i) to (iv) does not need to include two chemisorption reaction species P1 and P2 as in the previous example, and it does not even need to include a second reaction species, but may Apply these possibilities / selections depending on the desired deposition chemistry involved.

However, because of the limited nature of ALD, only a thin layer of material is deposited in a single cycle of ALD, and usually only a single molecular monolayer. For example, depending on the exposure time of the operation of dosing the thin film precursor and the sticking coefficients of the thin film precursor to the substrate surface, each ALD cycle deposits only a thin film layer with a thickness of about 0.5 to 3 Å, and therefore The operation sequence of the general ALD cycle (the aforementioned operations (i) to (iv)) is usually repeated multiple times to form a conformal film having a desired thickness. Therefore, in some embodiments, operations (i) to (iv) are repeated continuously, at least 1 time, or at least 2 times, or at least 3 times, or at least 5 times, or at least 7 times, or at least 10 times. . The rate of depositing an ALD film can be approximately or between 0.1 Å and 2.5 Å per ALD cycle, or approximately or between 0.2 Å and 2.0 Å per ALD cycle, or approximately or between 0.3 Å and 1.8 per ALD cycle. Å, or approximately 0.5 between Å and 1.5 Å per ALD cycle, or approximately 0.1 Å and 1.5 Å per ALD cycle, or approximately 0.2 Å and 1.0 Å per ALD cycle, or each ALD cycles are approximately or between 0.3 Å and 1.0 Å, or each ALD cycle is approximately or between 0.5 Å and 1.0 Å.

In some chemicals used to form thin films, in addition to those known as "thin film precursors", auxiliary reactants or co-reactants can also be used. In some such embodiments, the flow may be continuous during the subset of steps (i) to (iv), or the entire period of each of steps (i) to (iv) (when it is repeated). The co-reactant or co-reactant. In some embodiments, this additional reactive chemical species (auxiliary reactants or co-reactants, etc.) is adsorbed on the surface of the substrate before reacting with the thin film precursor (as described above including the precursors P1 and P2 Example), however, in other embodiments, the additional reactive chemical species reacts with the adsorbed thin film precursor (when the two are in contact), essentially without previous adsorption (adsorbed on the surface of the substrate) . Further, in some embodiments, the operation (iii) of reacting the adsorbed thin film precursor may include contacting the adsorbed thin film precursor with a plasma. The plasma can provide energy to drive a thin film formation reaction on the substrate surface. In some such embodiments, the plasma may be an oxidative plasma generated in a reaction chamber by applying a suitable RF power (but in some embodiments, it is generated remotely). In other embodiments, an inert plasma (instead of an oxidation plasma) may be used. The oxidizing plasma may be formed from one or more oxidizing agents (such as O ₂ , N ₂ O, or CO ₂ ), and it may be desirable to include one or more diluents (such as Ar, N ₂ , or He). ). In one embodiment, the oxidation plasma is formed of O ₂ and Ar. A suitable inert plasma may be formed from one or more inert gases, such as He or Ar. Further changes in ALD processing are detailed in previous patent applications cited above (and references incorporated herein).

Therefore, a basic operation sequence of forming a material thin film layer on a substrate through an ALD process is schematically illustrated by a flowchart in FIG. 5. As shown in the figure, the ALD process for forming a single thin film layer on the substrate begins at operation 115, which causes the thin film precursor to be adsorbed on the substrate, so that the precursor forms an adsorption limiting layer on the substrate; and then proceeds to operation 512. , Removing at least some unadsorbed film precursors from the volume surrounding the adsorbed precursors. Next, in operation 513, the adsorbed thin film precursor is reacted to form a thin film layer on the substrate. Finally, in some embodiments (such as those marked with a dashed box in FIG. 5), and depending on the chemical of the film formation reaction, operation 513 may be followed by operation 514 to remove the desorbed film precursor and / Or reaction byproducts are removed from the surrounding volume of the thin film layer (if present after the adsorbed precursor is reacted in operation 513).

The foregoing sequence of operations 511 to 514 represents a single ALD cycle, and the result is the formation of a single thin film layer. However, because a single thin film layer formed by ALD is typically very thin (usually only having a single molecule thickness), it is necessary to repeat the ALD cycle multiple times in succession to accumulate a thin film with a considerable thickness. Therefore, referring again to FIG. 5, if it is desired to deposit a thin film having, for example, N layers (or, similarly, the N layer of the thin film), the ALD cycle is repeatedly repeated multiple times (operations 511 to 514), and then in each cycle After ending with operation 514, in operation 515, it is determined whether N cycles of ALD have been performed. Then, if N cycles have been performed, the thin film formation operation is ended; otherwise, the processing sequence returns to operation 511 to start another cycle of ALD.

In some embodiments, a thin film deposited from multiple layers may include regions / sections of alternating composition that are formed by, for example, the following actions: Conformally depositing a plurality of layers (the plurality of layers depend on Sequentially having one composition), then depositing a plurality of layers conformally (the plurality of layers sequentially having another composition), and then possibly repeating and alternating the two sequences. These aspects of some deposited ALD films are described in, for example, US Patent Application No. 13/607386, filed on 9/7/2012, and entitled "CONFORMAL DOPING VIA PLASMA ACTIVATED ATOMIC LAYER DEPOSITION AND CONFORMAL "FILM DEPOSITION" (agent case number is NOVLP488), the case is incorporated in its entirety and its various uses for reference. Conformal films with alternating composition (including films used to penetrate underlying target IC structures or substrate regions) and more examples of methods for forming such films are described in detail in: U.S. Patent Application No. No. 13/084399, the filing date is 4/11/2011, and the case name is “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION” (Nominee Case No. NOVLP405); US Patent Application No. 13/242084, the filing date is 9/23 / 2011, and the case name is "PLASMA ACTIVATED CONFORMAL DIELECTRIC FILM DEPOSITION", and it is now US Patent No. 8637411 (Nominee NOVLP427); US Patent Application No. 13/224240, the application date is 9/1/2011, And the case name is "PLASMA ACTIVATED CONFORMAL DIELECTRIC FILM DEPOSITION" (the agent case number is NOVLP428); the US patent application is 13/607386, the filing date is 9/7/2012, and the case name is "CONFORMAL DOPING VIA PLASMA ACTIVATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION "(Attorney's case number is NOVLP488); and US Patent Application No. 14/194549, the filing date is 2/28/2014, and the case name is" CAPPED ALD FILMS " FOR DOPING FIN-SHAPED CHANNEL REGIONS OF 3-D IC TRANSISTORS "; each of these cases is incorporated by reference in its entirety and its various uses.

As detailed in the previously cited specification, ALD treatment is commonly used to deposit conformal silicon oxide (SiOx) films, however, as also disclosed in the previously cited specification, ALD treatment can also be used to deposit other chemicals Conformal dielectric film. In some embodiments, the dielectric film formed by ALD contains a silicon carbide (SiC) material, a silicon nitride (SiN) material, a silicon carbonitride (SiCN) material, or a combination thereof. In some embodiments, silicon-carbon-oxide, silicon-carbon-nitrogen compound, and silicon-carbon-nitride can also be formed in a thin film formed through ALD. Methods, techniques, and operations for depositing these types of thin films are described in detail in US Patent Application No. 13/494836, filed on 12/6/2012, and named "REMOTE PLASMA BASED DEPOSITION OF SiOC CLASS" OF FILMS ". The agent case number is NOLPLP466 / NVLS003722; US patent application number 13/907699, the filing date is 31/5/2013, the case name is "METHOD TO OBTAIN SiC CLASS OF FILMS OF DESIRED COMPOSITION AND FILM PROPERTIES", the agent case number LAMRP046 / 3149; U.S. Patent Application No. 14/062648, entitled "GROUND STATE HYDROGEN RADICAL SOURCES FOR CHEMICAL VAPOR DEPOSITION OF SILICON-CARBON-CONTAINING FILMS"; and U.S. Patent Application No. 14/194549, filed on 2 / 28/2014, and the case name is "CAPPED ALD FILMS FOR DOPING FIN-SHAPED CHANNEL REGIONS OF 3-D IC TRANSISTORS"; each of these cases is incorporated by reference in its entirety and its various uses.

Other examples of thin film deposition through ALD (including chemicals used to deposit dopant-containing films) are described in the patent applications listed above and incorporated in the reference (US Patent Application Nos. 13/084399, 13 / 242084, 13/224240, and 14/194549). As contained therein, a variety of dopant-containing film precursors can be used to form dopant-containing films, such as boron-doped silicate glass (BSG) films, phosphorus-doped silicate glass ( (PSG) films, borosilicate-doped silicate glass (BPSG) films, arsenic (As) -doped silicate glass (ASG) films, and other films. The dopant-containing film may include B ₂ O ₃ , B ₂ O, P ₂ O ₅ , P ₂ O ₃ , As ₂ O ₃ , As ₂ O ₅ , and other films. Therefore, dopant-containing films having other dopants other than boron are also feasible. Examples include gallium, phosphorus, or arsenic dopants, or other elements suitable for doping semiconductor substrates, such as other III- and V-valent elements.

Regarding the process conditions of ALD, ALD processing can be performed at various temperatures. In some embodiments, a suitable temperature range within the ALD reaction chamber may be between about 25 ° C and 450 ° C, or between about 50 ° C and 300 ° C, or between about 20 ° C and 400 ° C or Between about 200 ° C and 400 °, or between about 100 ° C and 350 ° C.

Similarly, ALD can be performed under a variety of ALD reaction chamber pressures. In some embodiments, a suitable pressure range within the reaction chamber may be between about 10 mTorr and 10 Torr, or between about 20 mTorr and 8 Torr, or between about 50 mTorr and 5 Tor, or between about 100 mTorr and 2 Torr.

If a plasma is used in operation (iii), multiple RF power levels can be applied to generate the plasma. In some embodiments, a suitable RF power range may be between about 100 W and 10 kW, or between about 200 W and 6 kW, or between about 500 W and 3 kW, or between about 1 Kw and 2 kW .

A variety of flow rates for the film precursor can be applied in operation (i). In some embodiments, a suitable flow rate range may be about or between 0.1 mL / min to 10 mL / min, or about or between 0.5 mL / min and 5 mL / min, or about or between 1 mL / min and 3 mL / min.

Various flow rates of gas can be used in various operations. In some embodiments, the total gas flow rate range can be about or between 1 L / min and 20 L / min, or about or between 2 L / min and 10 L / min. For the optional inert flushing steps in operations (ii) and (iv), the burst flow rate range applied may be about or between 20 L / min and 100 L / min, or about or between 40 L / min With 60 L / min.

In some embodiments, the step of pumping to the base pressure again refers to pumping the reaction chamber to the base pressure by directly exposing it to one or more vacuum pumps. In some embodiments, the base pressure is typically only a few millitorr (eg, between about 1 and 20 mTorr). Furthermore, as noted previously, the step of pumping to the base pressure may or may not be accompanied by inert flushing, and therefore, when one or more valves open the conduction path to the vacuum pump, the carrier gas may or may not flow.

Again, multiple ALD cycles can be repeated to accumulate a stack of conformal layers. In some embodiments, the layers have substantially the same composition, however, in some embodiments, the layers sequentially deposited through ALD may have different compositions, or in some such embodiments, the composition may be Alternate layers, or layers with different compositions have a repetitive sequence, as described earlier. Therefore, according to embodiments, specific lamination engineering concepts can be used to modulate the concentration of boron, phosphorus, or arsenic in the film, such as the patent application listed previously and incorporated by reference (US Patent Application No. 13/084399 No. 13/242084 and 13/224240). [Embodiment of substrate processing equipment]

The methods described herein may be performed by any suitable semiconductor substrate processing equipment. Appropriate equipment includes hardware for performing processing operations, and a system controller with instructions for controlling the processing operations in accordance with the various access methods disclosed herein. In some embodiments, the hardware may include one or more processing stations included in a multi-station substrate processing tool; and a controller with (or available) machine-readable instructions, The controller is used to control the processing operations according to the processing techniques disclosed herein.

Therefore, in some embodiments, a device suitable for depositing a thin film of material on a plurality of semiconductor substrates may include a first set of one or more processing stations, each processing station having a substrate holder and accommodating a processing In the chamber; a second set of one or more processing stations, each of which has a substrate holder and is housed in the processing chamber; one or more valves for controlling the film precursors to the The flow rate of the processing stations; and one or more valve-driven vacuum sources for removing film precursors from the surrounding volume of the processing stations (contained in the processing chamber). And, such equipment also includes a controller with (or available) machine-readable instructions for operating a substrate loading device, a substrate transfer device, one or more valves, and a vacuum source to deposit a thin film of material On these substrates.

Therefore, in some embodiments, the instructions executed by the controller may include instructions for forming a thin film on a plurality of substrates in a plurality of processing stations (accommodated in a processing chamber), wherein the plurality of thin films Layers are formed on each substrate through a series of ALD cycles. Therefore, in some such embodiments, the instructions executed by the controller may include instructions for performing ALD operations (i) to (iv) (as described above), and for repeating ALD operations (i) To (iv) multiple instructions to form a plurality of thin film layers on the plurality of substrates (in the plurality of processing stations in the substrate processing equipment).

Therefore, FIG. 1 schematically shows an embodiment of the substrate processing apparatus 100. For clarity, the processing device 100 is depicted as a single-station processing device having a body of a processing chamber 102 to maintain a low-pressure environment. It should be appreciated, however, that a common processing tool environment (eg, in a common reaction chamber) may include multiple processing stations, as described herein. For example, Figure 2 depicts one embodiment of a multi-station processing tool. Furthermore, it should be noted that in some embodiments, one or more hardware parameters of the processing device 100 can be programmatically adjusted through one or more system controllers (including those discussed in detail above).

The processing equipment 100 is in fluid communication with the reactant delivery system 101 to deliver the processing gas to the distributed showerhead 106. The reactant delivery system 101 includes a mixing vessel 104 for mixing and / or conditioning the process gas delivered to the showerhead 106. One or more mixing vessel inlet valves 120 may control the introduction of process gas into the mixing vessel 104.

Some reactants are stored in a liquid form before being vaporized and successively transferred to the processing chamber 102. The embodiment in FIG. 1 includes a vaporization point 103 for vaporizing a liquid reactant to be supplied to the mixing container 104. In some embodiments, the vaporization point 103 may be a heated liquid injection module. In some embodiments, the vaporization point 103 may be a heating vaporizer. Without proper controls (eg, helium is not used when vaporizing / nebulizing liquid reactants), the saturated reactant vapors generated by such modules / vaporizers may condense in downstream delivery piping systems. Exposure of incompatible gases to this reactant that has condensed may produce particulates. Such particles may block the piping system, prevent valve operation, and contaminate the substrate. Some approaches to address these issues include purifying and / or emptying the delivery piping system to remove residual reactants. However, purifying the transportation piping system increases the cycle time of the processing station, resulting in a reduction in the output of the processing station. Therefore, in some embodiments, the transportation piping system downstream of the vaporization point 103 is heat-treated. In some examples, the mixing vessel 104 is also heat treated. In a non-limiting example, the piping system downstream of the vaporization point 103 has an increased temperature profile, extending from about 100 ° C to about 150 ° C in the mixing vessel 104.

As mentioned above, in some embodiments, the vaporization point 103 may be a heated liquid injection module (referred to as a "liquid injector"). Such a liquid injector can inject a pulse of liquid reactant into a carrier gas stream upstream of the mixing vessel. In one approach, the liquid injector can vaporize the reactants by abruptly moving the liquid from high pressure to low pressure. In another solution, the liquid injector can atomize the liquid into dispersed micro-droplets, and then the micro-droplets are successively vaporized in a heated delivery piping system. It should be noted that the smaller droplets vaporize faster than the larger droplets, so the delay time between injecting the liquid and completing the vaporization is shortened. Faster vaporization can shorten the length of the piping system downstream of the vaporization point 103. In one solution, the liquid injector can be directly mounted on the mixing container 104. In another solution, the liquid injector can be directly mounted on the shower head 106.

In some embodiments, a liquid flow controller (LFC) is provided upstream of the vaporization point 103 to control the mass flow of the liquid to be vaporized and delivered to the processing chamber 102. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A feedback control signal is provided by a proportional-integral-derivative (PID) controller electrically connected to the MFM, and then the plunger valve of the LFC can be adjusted to respond to the feedback control signal. However, it takes 1 second or more to stabilize the flow using the feedback control. This will prolong the time to pour in the liquid reactant. Therefore, in some embodiments, the LFC can dynamically switch between feedback control mode and direct control mode. In some embodiments, the LFC dynamically switches from the feedback control mode to the direct control mode by stopping the sensing circuit of the LFC and the PID controller.

The shower head 106 distributes the processing gas and / or reactants (such as thin film precursors) to the substrate 112 in the processing station, and the flow rate of the processing gas and / or reactants is determined by one or more upstream of the shower head. Valves (such as valves 120, 120A, 105). In the embodiment shown in FIG. 1, the substrate 112 is located below the shower head 106 and appears to be placed on the support 108. It should be appreciated that the showerhead 106 may have any suitable shape and may have any suitable number and configuration of ports to distribute the processing gas onto the substrate 112.

In some embodiments, a microvolume 107 is located below the showerhead 106. In a micro-volume of the processing station, performing ALD processing near the substrate (instead of the entire volume of the processing chamber) can shorten the time for reactant exposure and purification, and can change process conditions (such as pressure, temperature, etc.) Time, which limits the time that the processing station machine is exposed to the processing gas, etc. Exemplary microvolume sizes include, but are not limited to, volumes between 0.1L and 2L.

In some embodiments, the support 108 may be raised or lowered to expose the substrate 112 to the microvolume 107 and / or change the volume of the microvolume 107. For example, during the substrate transfer stage, the support 108 may be lowered to allow the substrate 112 to be loaded onto the support 108. During the deposition processing stage on the substrate, the support 108 may be raised to position the substrate 112 in the microvolume 107. In some embodiments, the microvolume 107 may completely surround the substrate 112 and a portion of the support 108 to establish a region of high flow impedance during the deposition process.

Alternatively, the support 108 may be lowered and / or raised during part of the deposition process to adjust the processing pressure, reactant concentration, etc. within the micro-volume 107. In one scenario where the body of the processing chamber 102 is maintained at a base pressure during processing, the support 108 is lowered to allow the microvolume 107 to be evacuated. Exemplary ratios of microvolume ratio to processing chamber volume include, but are not limited to, volume ratios between 1: 500 and 1:10. It should be noted that, in some embodiments, the height of the support can be programmatically adjusted through a suitable system controller.

In another approach, adjusting the height of the support 108 may allow the plasma density to be changed during plasma activation and / or processing cycles (included in, for example, an ALD or CVD process). At the end of the deposition process phase, the support 108 may be lowered during another substrate transfer phase to allow the substrate 112 to be removed from the support 108.

Although the exemplary microvolume changes described herein involve a height-adjustable stand, it should be understood that in some embodiments, the position of the showerhead 106 can be adjusted relative to the stand 108 to change the microvolume 107 The volume. Furthermore, it should be understood that the vertical position of the support 108 and / or the shower head 106 can be changed by any suitable mechanism in the field of the present invention. In some embodiments, the support 108 may include a rotation axis for rotating the direction of the substrate 112. It should be noted that in some embodiments, one or more such exemplary adjustments may be performed programmatically by one or more suitable system controllers, and the system controllers may be used to perform the foregoing Machine-readable instructions for all or a subset of operations.

Returning to the embodiment shown in FIG. 1, the shower head 106 and the support 108, and the RF power supply 114 and the matching network 116 are electrically connected to apply power to the plasma. In some embodiments, the energy of the plasma is controlled by controlling one or more of the processing station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse duration (e.g., by having a suitable A system controller of machine-readable instructions). For example, the RF power supply 114 and the matching network 116 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are listed above. As such, the RF power supply 114 may provide RF power having any suitable frequency. In some embodiments, the RF power supply 114 may be configured to control high and low frequency RF power sources (the two power sources are independent of each other). Exemplary low frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 500 kHz. Exemplary high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It should be known that any suitable parameter can be adjusted discontinuously or continuously to provide plasma energy to the surface reaction. In a non-limiting example, the plasma power is pulsed intermittently (as opposed to continuously applying power to the plasma) to reduce ion bombarment with the substrate surface.

In some embodiments, the plasma may be detected in situ by one or more plasma detectors. In one solution, the plasma power is detected by one or more voltage and current sensors (such as VI probes). In another solution, the density of the plasma and / or the concentration of the processing gas is measured by one or more optical emission spectroscopy (OES) sensors. In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such an in-situ plasma detector. For example, OES sensors can be used in a feedback loop to provide programmed control of plasma power. It should be noted that in some embodiments, other detectors may be used to detect the plasma and other process characteristics. Such detectors may include, but are not limited to, infrared (IR) detectors, sonic detectors, and pressure gauges.

In some embodiments, the plasma can be controlled by input / output control (IOC) continuous instructions. In an example, the instruction for setting the plasma state in the plasma activation phase may be included in a corresponding plasma activation formula phase of a process recipe. In some examples, the process recipe phases may be arranged in a time series such that all instructions for a process phase are performed simultaneously with the process phase. In some embodiments, the instructions for setting one or more plasma parameters may be included in a formulation stage prior to the plasma processing stage. For example, the first recipe stage may include an instruction to set an inert (eg, helium) and / or reaction gas flow rate, an instruction to set a plasma generator to a power setting, and a delay time instruction for the first recipe stage. The subsequent second recipe phase may include instructions to operate the plasma generator, and a delay time instruction for the second recipe phase. The third recipe phase may include an instruction to stop the plasma generator and a delay time instruction for the third recipe phase. It should be understood that these formulation stages can be further subdivided and / or repeated in any suitable manner within the scope of the present invention.

In some deposition processes, plasma strikes take a duration of about a few seconds or more. In certain embodiments described herein, a more transient plasma impact may be applied during a processing cycle. This can be about 50 milliseconds to 1 second, and the specific example is 0.25 seconds. Such transient RF plasma shocks require rapid stabilization of the plasma. In order to achieve rapid stabilization of the plasma, the plasma generator can be configured so that the impedance matching value is preset to a specific voltage value, but the frequency is allowed to float. Traditionally, high-frequency plasmas are generated at an RF frequency of about 13.56 MHz. In many embodiments disclosed herein, the frequency is allowed to float to a value different from this standard value. By allowing the frequency to float while fixing the impedance matching value to a preset voltage value, the plasma can be stabilized more quickly. The rapid stabilization of the plasma is useful for the very short duration of the plasma shock associated with the ALD cycle. important.

In some embodiments, the support 108 may control the temperature through the heater 110. Furthermore, in some embodiments, pressure control is provided to the processing device 100 through one or more valve-driven vacuum sources (eg, butterfly valve 118). As shown in the embodiment of FIG. 1, the butterfly valve 118 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, the pressure control of the processing apparatus 100 may also be adjusted by changing the flow rate of one or more gases introduced into the processing chamber 102. In some embodiments, one or more valve-driven vacuum sources (eg, butterfly valve 118) may be used to remove film precursors from the volume surrounding the processing station during a suitable ALD operational phase.

As described above, one or more processing stations may be included in a multi-station substrate processing tool. FIG. 2 schematically depicts an example of a multi-station processing tool 200 that includes a plurality of processing stations 201, 202, 203, 204 in a common low-pressure processing chamber 214. By maintaining the stations in a low-pressure environment, defects caused by breaking the vacuum between thin film deposition processes can be avoided.

As shown in FIG. 2, the multi-station processing tool 200 has a substrate loading port 220 and a substrate handling machine 226 configured to move substrates from a cassette loaded through a container 228, move through the substrate loading port 220, and enter a processing chamber. 214, and finally placed on a processing station. Specifically, in this example, the substrate transfer machine 226 loads substrates into the processing stations 201, 202, and the substrate transfer device (in this example, the substrate rotation rack 290) is at a plurality of processing stations 201, 202, and 203 And 204 transfer substrates. In the embodiment shown in FIG. 2, the substrate loading device is depicted as a substrate handling machine 226 having two arms (for the manipulation of the substrate), so as depicted, it can load substrates into stations 201 and 202. On (possibly simultaneously, or sequentially). Next, after the substrate is loaded on the stations 201 and 202, the substrate transfer device (the rotary rack 290 depicted in FIG. 2) can be rotated 180 degrees (along its central axis, which is substantially perpendicular to the plane of the substrate (convex) Paper surface) and substantially the same distance from the substrates) to transfer 2 substrates from stations 201 and 202 to stations 203 and 204. At this time, the handling machine 226 can load two new substrates onto the stations 201 and 202 to complete the loading process. These steps can be reversed for unloading. In addition, to process the 4 wafers of the complex array, before rotating the transfer rotary rack 290 by 180 degrees, unload the 2 substrates through the conveying machine 226 each time. , Accompanied by the loading of two new substrates. Similarly, in the 4-step loading process, a single-armed handling machine (which is configured to place the substrate at only one station, such as station 201) can be used, with four 90-degree rotations of the rotating rack 290, to The substrate is loaded into all 4 stations.

Shown in FIG. 2, the processing chamber 214 is drawn to provide four processing stations 201, 202, 203, and 204. Each station has a heated support (see, for example, support 108 in Figure 3) and a gas line inlet. It should be noted that, in some embodiments, each processing station may have different or multiple functions. For example, in some embodiments, the processing station may switch between an ALD processing mode and a CVD processing mode. Additionally or alternatively, in some embodiments, the processing chamber 214 may include one or more pairs of ALD / CVD processing stations. Although the depicted processing chamber 214 contains 4 processing stations, it should be noted that a processing chamber according to the present invention may have any suitable number of stations. For example, in some embodiments, a processing chamber may have 1, or 2, or 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11, or 12, or 13 , Or 14, or 15, or 16, or more processing stations (or a set of embodiments may be depicted as having a number of processing stations in a range in each reaction chamber, the range being Defined by a pair, such as 2 to 6 processing stations in each reaction chamber, or 4 to 8 processing stations in each reaction chamber, or 8 to 16 in each reaction chamber Processing station, etc.).

As noted previously, FIG. 2 depicts an embodiment of a substrate transfer apparatus 290 for transferring substrates among processing stations 201, 202, 203, and 204 (located in processing chamber 214). It should be noted that any suitable substrate transfer device can be applied. Non-limiting examples include wafer rotating racks, and substrate handling machines. [Detailed description of sprinkler head and sprinkler sleeve]

In the ALD process, in the reaction chamber, the thin film precursors must be alternately present and then evacuated. To avoid parasitic deposition, excess precursors in the processing chamber are removed from the processing chamber and a common precursor path (such as the stem of a showerhead) before introducing the next precursor. The inert gas is usually used to clean the conveying path and the chamber to remove excess precursors. However, when a chandelier-type showerhead is used, the cleaning gas from the shower head cannot effectively remove excess precursors that are stuck on the back side of the showerhead. As a result, the precursor may produce a significant amount of parasitic deposits on the backside of the showerhead, the top plate, and the walls of the processing chamber. It is not possible to fill the dead space with a solid dielectric, as this method may cause RF ground coupling problems. Therefore, as described above, the introduction of a secondary cleaning gas from the back side of the shower head can be applied to avoid such parasitic deposition. The hardware used to perform this secondary cleaning will now be described in detail:

Referring now to FIG. 6, an example of a substrate processing system 650 including a processing chamber 660 having a showerhead 670 is shown. The shower head includes a stem 672 and a head 674. The head 674 defines an inner cavity 675. Fluid, such as precursors or cleaning gas, flows through the stem 672, reaches the distribution plate 676, and enters the inside cavity 675. The fluid then passes through holes / spacers 678 in the bottom surface of the head 674 and enters the processing chamber 660.

The rod 672 of the shower head 670 is connected to the top chamber wall of the processing chamber 660 through the shower head bushing 680. The shower head sleeve 680 has a substantially "T" -shaped cross section, and includes a head portion 681 and a rod portion 683. The showerhead sleeve 680 defines a cylindrical inner cavity 684, and the inner cavity 684 receives a rod portion 672 of the showerhead 670. A plurality of slot-shaped holes 686 are formed in the rod portion 683 so that the secondary cleaning gas can flow from the inner cavity 684 to the outer surface of the rod portion 683. It can be understood from the direction of the slot-shaped hole 686 in FIG. 6 and the secondary cleaning flow path 320 shown in FIG. 3 that the secondary cleaning gas flows into the processing chamber in a direction substantially parallel to the plane of the substrate. (But the direction of flow changes near the walls of the chamber, as shown in Figure 3).

A fluid connector 690 is connected to the edge of the head 681 of the showerhead sleeve 680, and the fluid connector 690 is used to supply a fluid (e.g., a cleaning gas). The fluid connector 690 includes one or more conduits and / or fittings generally designated at 692. The head 681 of the showerhead sleeve 680 also includes a conduit and / or a connector generally designated 693 to direct the flow of fluid into the inner cavity 684 of the showerhead sleeve 680.

The flat plate 700 is disposed between the head 674 of the shower head 670 and the shower head sleeve 680. The plate 700 includes an upper surface 704, a central opening or hole 710, and a bottom surface 714. In some examples, the plate 700 is made of ceramic. The thickness of the plate 700 can be selected to minimize material and capacitive coupling to the ground or parasitic plasma. The upper surface 704 of the plate 700 is spaced from the bottom edge of the showerhead sleeve 680 to allow fluid to pass therethrough. The center hole 710 also maintains a distance from the rod portion 672 to allow fluid to pass therethrough. The bottom surface 714 of the plate 700 is spaced from the upper surface of the shower head 670 to allow fluid to pass therethrough. In some examples, the plate 700 may be omitted, and the processing chamber may be operated without the plate 700.

Flowing the secondary cleaning gas through the shaft sleeve can prevent the deposited chemicals from entering the cavity area, thereby avoiding the unfavorable film deposition effect there. The size of these notches and other pores can be selected to avoid plasma ignition in them, and to allow the matching conditions to avoid reverse diffusion and obtain the desired gas flow rate.

Referring now to FIG. 7, an example of a showerhead sleeve 680 is shown. The shower head sleeve 680 includes a head portion 681 and a rod portion 683. The notch 686 may have an arc shape and be disposed around the rod portion 683. The notch 686 allows fluid to flow through the notch 686 from the inside cavity 684. The head 681 includes an engaging portion 718 that engages with a corresponding one of the fluid connectors 690. When connected, the conduit 693 of the sprinkler sleeve 680 is aligned with the conduit 692 of the fluid connector 690.

Referring now to FIG. 8, an example of a fluid connector 690 for a showerhead bushing 680 is shown. Although the fluid connector 690 is shown as including a second joint 720, a conduit 730, a joint 732, a conduit 734, and a joint 736, other configurations of the fluid connector are contemplated.

9A and 9B, an example of the tablet 700 is shown. In FIG. 9A, the upper surface 704 of the flat plate 700 is shown as having a substantially circular cross section and a center hole 710 provided in the center of the flat plate 700. The central hole 710 includes one or more raised portions 740 that extend radially inward from the central hole 710. The raised portion 740 provides a uniform distance between the flat plate 700 and the rod portion 672. In FIG. 9B, the bottom surface 714 of the plate 700 is shown to include a raised portion 744 that extends downward (relative to the top of the processing chamber). The raised portion 744 provides a uniform distance between the bottom surface 714 of the flat plate 700 and the upper surface of the head 674 of the shower head 670. It is also noted that the RF isolation / suppression device can reduce the electric field in the cavity on the back side of the shower head, which also helps to further reduce the chance or degree of parasitic plasma generated in the back side area of the shower head. . For example, the distance provided by the protrusions 740 and 744 is close enough to reduce parasitic plasma generation, for example, if a distance of about 3 mm or less is applied. In terms of general process conditions, such a distance is not enough to allow the plasma and the plasma sheath to form together (less than 2 plasma sheath lengths). Plasma formation is affected by the density of the plasma, the electron temperature of the plasma, and the trans-pressure of the plasma sheath. Of course, as discussed in detail above, using O ₂ as a secondary cleaning gas is also an effective technique to avoid / minimize parasitic plasma generation. [System controller]

FIG. 2 also depicts an embodiment of a system controller 250 for controlling process conditions and hardware states of the processing tool 200 and its processing station. The system controller 250 may include one or more memory devices 256, one or more mass storage devices 254, and one or more processors 252. The processor may include one or more CPUs, ASICs, general purpose computers, and / or special purpose computers, one or more analog and / or digital input / output connections, one or more stepper motor controls Board, etc.

In some embodiments, the system controller 250 controls one or more operations of the processing tool 200, including operations of its individual processing stations. The system controller 250 may execute machine-readable system control instructions 258 on the processor 252; in some embodiments, the system control instructions 258 are loaded from the mass storage device 254 into the memory device 256. System control instructions 258 include instructions to control: time history, mixing of gaseous and liquid reactants, chamber and / or station pressure, wafer temperature, target power level, RF power level, RF exposure time , The positioning of the substrate support, the suction cup, and / or the receiver, and other process-specific parameters performed by the processing tool 200. These processes include many types of processes, including (but not limited to) processes related to film deposition on a substrate. The system control instructions 258 may be configured in any suitable manner. For example, subroutines or control objects of many processing tool components can be written to control the operation of the processing tool components required to implement the processing of many processing tools. System control instructions 258 may be encoded in any suitable computer-readable programming language. In some embodiments, the system control instructions 258 are executed in software, in other embodiments the system control instructions 258 are executed in hardware, such as hard-coded into logic in an ASIC (Application Specific Integrated Circuit), or In other embodiments, it is implemented as a combination of software and hardware.

In some embodiments, the system control software 258 may include input / output control (IOC) sequence instructions to control many of the parameters described above. For example, each stage of the deposition process may include one or more instructions executed by the system controller 250. For example, the instructions for setting the process conditions of the thin film deposition process stage may be included in the corresponding deposition recipe stage, and the steps for the capping thin film deposition process are similar. In some embodiments, the recipe phases may be arranged sequentially such that all instructions for a process phase are executed simultaneously with the process phase.

In some embodiments, other computer-readable instructions and / or programs may be used, which are stored in a mass storage device 254 and / or a memory device 256 connected to the system controller 250. Examples of programs or program sections include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

The substrate positioning program includes instructions for processing tool components, which are used to load a substrate onto a support, and to control the distance between the substrate and other components of the processing tool 200. The positioning program includes instructions to appropriately move the substrate into or out of the reaction chamber as needed to deposit a thin film on the substrate.

The process gas control program includes instructions for controlling the composition and flow rate of the gas, and optionally used to flow the gas into the surrounding volume of one or more processing stations prior to deposition to stabilize the pressure in those volumes. . In some embodiments, the process gas control program includes instructions to introduce certain gases into a surrounding volume of one or more processing stations (located in a processing chamber) during thin film deposition on a substrate. The process gas control program also includes instructions for delivering the gases at the same rate and at the same time (or at different rates and / or at different times) based on the composition of the deposited film. The process gas control program also includes instructions for atomizing / vaporizing a liquid reactant in a heating injection module in the presence of helium or some other carrier gas.

The pressure control program includes instructions for controlling the pressure in the processing station, for example, by adjusting a throttle valve of an emptying system of the processing station, allowing gas to flow into the processing station, and the like. The pressure control program includes instructions to maintain the same or different pressures during the deposition of many film types on a substrate.

The heater control program includes instructions for controlling a current to a heating element used to heat the substrate. Alternatively or additionally, the heater control program controls the delivery of a heat transfer gas (such as helium) to the substrate. The heater control program includes instructions to maintain the same or different temperatures in the surrounding volume of the reaction chamber and / or processing station during the deposition of many film types on a substrate.

The plasma control program includes instructions for setting the RF power level, frequency, and exposure time in one or more processing stations according to embodiments herein. In some embodiments, the plasma control program includes instructions for using the same or different RF power levels, and / or frequencies, and / or exposure times during film deposition on the substrate.

In some embodiments, there is a user interface connected to the system controller 250. The user interface includes a display screen, an icon software display of the device and / or process conditions, and a user input device (such as a pointing device, a keyboard, a touch screen, a microphone, etc.).

In some embodiments, the parameters adjusted by the system controller 250 are related to process conditions. Non-limiting examples include: composition and flow rate, temperature, pressure, plasma state (such as RF bias power level and exposure time) of the process gas, and the like. These parameters can be provided to the user in the form of a recipe (which can be entered by a user interface).

Through the analog and / or digital input connections of the system controller 250, signals from a variety of processing tools can be used to monitor the process. The signals used to monitor the process can be output on the analog and / or digital output connectors of the processing tool 200. Non-limiting examples of sensors that can be monitored for processing tools include mass flow controllers (MFCs), pressure sensors (eg, pressure gauges), thermocouples, and the like. Process conditions can be maintained along with data from such sensors using appropriately programmed feedback and control algorithms.

The system controller 250 provides machine-readable instructions to perform the deposition process described above. These instructions can control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. According to various embodiments described herein, the instructions may control the parameters to perform in-situ deposition of the thin film stack.

The system controller typically includes one or more memory devices and one or more processors, the configuration of which is configured to execute machine-readable instructions to cause the device to perform operations according to the processes disclosed herein. A machine-readable, non-transitory medium containing instructions for controlling a substrate doping process operation in accordance with the disclosure herein may be coupled to the system controller.

Many of these devices and methods described above can be used in conjunction with lithographic patterning tools and / or processes, such as for the processing or manufacturing of semiconductor devices, displays, LEDs, solar panels, and the like. Typically, but not necessarily, such tools or processes can be used together and / or simultaneously in a common manufacturing facility.

The lithographic patterning of a film typically includes some or all of the following operations, each of which is facilitated by a number of reasonable tools: (1) coating a photoresist on a substrate (such as a silicon nitride formed on top) Thin film substrate), using spin coating or spraying tools; (2) hardening the photoresist, using a hot plate or furnace or other suitable hardening tools; (3) exposing the photoresist to visible light or UV light or X Light, using a tool such as a wafer stepper; (4) developing the photoresist to selectively remove and pattern the photoresist, using, for example, a wet cleaning table or spraying the developer Tools; (5) transfer the photoresist pattern to the underlying film or substrate, using dry or plasma-assisted etching tools; and (6) remove the photoresist and use, for example, RF or microwave plasma photoresist to peel off Tools. In some embodiments, before applying the photoresist, an ashable hard mask layer (such as an amorphous carbon layer) and other suitable hard mask (such as an anti-reflective layer) are deposited. [Other embodiments]

Although the aforementioned technologies, operations, processes, methods, systems, equipment, tools, films, chemicals, and compositions have been described in detail in the context of specific embodiments in order to improve clarity and understanding, but for the field of the present invention It is obvious to those having ordinary knowledge that there are many alternative ways of implementing the foregoing embodiments within the spirit and scope of the present invention. Therefore, the embodiments disclosed herein should be considered as illustrative disclosures (not restrictive) of the inventive concept, and should not be used as a basis for improperly limiting the scope of any patent application (which ultimately points to the subject matter of the invention).

100‧‧‧treatment equipment

101‧‧‧ Conveying System

102‧‧‧ Chamber

103‧‧‧Vaporization point

104‧‧‧mixing container

105‧‧‧ valve

106‧‧‧Sprinkler

107‧‧‧microvolume

108‧‧‧ substrate holder / support

110‧‧‧heater

112‧‧‧ substrate

114‧‧‧RF Power Supply

116‧‧‧ matching network

118‧‧‧Vacuum Pump / Butterfly Valve

120‧‧‧ Valve

120A‧‧‧Valve

150‧‧‧controller

200‧‧‧Processing equipment / processing tools

201‧‧‧Station

202‧‧‧Station

203‧‧‧station

204‧‧‧Station

214‧‧‧Processing chamber

220‧‧‧ substrate loading port

226‧‧‧handling machinery

228‧‧‧container

250‧‧‧ Controller

252‧‧‧Processor

254‧‧‧mass storage device

256‧‧‧Memory device

258‧‧‧System Control Instructions

290‧‧‧Rotating material rack

300‧‧‧ substrate processing equipment

303‧‧‧cross plate

310‧‧‧ flow path

312‧‧‧Purge gas source once

320‧‧‧ flow path

322‧‧‧ secondary cleaning gas source

330‧‧‧ sprinkler bushing

511‧‧‧operation

512‧‧‧operation

513‧‧‧ Operation

514‧‧‧operation

515‧‧‧ operation

650‧‧‧ substrate processing system

660‧‧‧Processing chamber

670‧‧‧ sprinkler

672‧‧‧ lever

674‧‧‧Head

675‧‧‧ inside cavity

676‧‧‧ distribution board

678‧‧‧hole

680‧‧‧ sprinkler sleeve

681‧‧‧Head

683‧‧‧pole

684‧‧‧Inner cavity

686‧‧‧Slotted hole / notch

690‧‧‧fluid connector

692‧‧‧ catheter

693‧‧‧ catheter

700‧‧‧ tablet

704‧‧‧upper surface

710‧‧‧center hole

714‧‧‧ bottom surface

718‧‧‧Joint

720‧‧‧Second Joint

732‧‧‧connector

734‧‧‧ catheter

736‧‧‧connector

740‧‧‧ raised

FIG. 1 is a schematic cross-sectional view of a substrate processing apparatus (including a single processing station) having a processing chamber.

2 is a schematic diagram of a four-station substrate processing apparatus having a substrate handling machine and a controller, where the substrate handling machine is used to load and unload substrates from two processing stations, and the controller is used to operate the substrate device.

3 is a schematic cross-sectional view of a processing chamber of a single-station substrate processing equipment having a shower head and a shower head sleeve, and the figure depicts the flow paths of the primary and secondary cleaning gases.

FIG. 4 is a plot of deposition rate and RF power, which is used to illustrate the presence and intensity of parasitic plasma (formed on the backside of the showerhead formed in the processing chamber).

FIG. 5 is a flowchart of an exemplary operation sequence for forming a thin film of material on a substrate through an ALD process.

FIG. 6 is a more detailed cross-sectional view of the shower head and the shower head sleeve in the substrate processing chamber, and the figure also depicts the flow paths of the primary and secondary cleaning gases.

FIG. 7 is a perspective view of an example of a showerhead sleeve.

FIG. 8 is a perspective view of an exemplary fluid connector for the showerhead bushing of FIG. 7. FIG.

9A and 9B are top and bottom plan views of an exemplary plate of the showerhead of FIG. 6.

Claims (24)

A method for depositing a thin film of material on a semiconductor substrate in a processing chamber, the method includes the following steps: (a) flowing a thin film precursor into the processing chamber; (b) causing the thin film precursor to be adsorbed on the processing chamber On the substrate in the chamber, so that the precursor forms an adsorption limiting layer on the substrate; (c) cleaning the processing chamber by using a cleaning gas once, at least a number of unadsorbed thin film precursors are adsorbed from And (d) removing the non-adsorbed precursor using the primary purge gas in step (c), while flowing a secondary purge gas into the processing chamber, Reacting the adsorbed thin film precursor to form a thin film layer on the substrate; wherein the secondary cleaning gas includes chemical species having free energy and / or dissociation energy equal to or greater than O ₂ . For example, the method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 1 of the application, wherein the secondary cleaning gas is O ₂ . For example, the method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 1 of the application, wherein the primary cleaning gas is an inert gas. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 3 of the application, wherein the primary cleaning gas is Ar and / or N ₂ . For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber as described in the first patent application scope, wherein the one-time cleaning gas does not flow into the processing chamber during steps (a)-(b) or (d) Room. For example, the method of claim 5 for depositing a thin film of material on a semiconductor substrate in a processing chamber, wherein before step (d), substantially all of the primary cleaning gas has been removed from the processing chamber. A method for depositing a thin film of a material on a semiconductor substrate in a processing chamber, such as in item 1 of the patent application scope, wherein during steps (a)-(d), the secondary cleaning gas is continuously flowed into the processing chamber in. The method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 1 of the patent application, wherein in step (a), the thin film precursor is flowed into the processing chamber using a carrier gas flow. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 8 of the application, wherein the carrier gas is an inert gas. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 9 of the application, wherein the carrier gas is N ₂ and / or Ar. The method for depositing a thin film of a material on a semiconductor substrate in a processing chamber as in any of claims 1-10 of the scope of patent application, further comprising: (e) after the adsorbed precursor reacts with the presence of When the attached film precursor and / or reaction by-product are used, the processing chamber is cleaned by using the one-time cleaning gas to remove the desorbed film precursor and / or reaction by-product from the surrounding volume of the film layer. The method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to any one of claims 1-10, further includes repeating steps (a)-(d) one or more times to Other thin film layers are deposited on the substrate. A method for depositing a thin film of a material on a semiconductor substrate in a processing chamber as in any of claims 1-10, wherein in step (a), the thin film precursor flows into the through a shower head. In the processing chamber, and in step (c), the primary cleaning gas flows into the processing chamber through the same shower head. For example, the method of claim 13 for depositing a thin film of material on a semiconductor substrate in a processing chamber, wherein the shower head includes a head portion and a rod portion, and wherein the primary cleaning gas passes through the shower head. A hole in the bottom surface of the head flows into the processing chamber. A method for depositing a thin film of a material on a semiconductor substrate in a processing chamber as in any of claims 1-10, wherein the primary cleaning gas flows into the substrate in a direction substantially perpendicular to a plane of the substrate. In the processing chamber. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber such as the scope of application for a patent, wherein the one-time cleaning gas flows into the processing chamber at a rate of about 5000 to 45000 sccm. For example, the method of claim 13 for depositing a thin film of material on a semiconductor substrate in a processing chamber, wherein the secondary cleaning gas system flows into the processing chamber through a shower nozzle sleeve. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber according to item 17 of the application, wherein the showerhead sleeve includes a head portion and a rod portion, and the secondary cleaning gas passes through the second cleaning gas. A hole in the shaft flows into the processing chamber. For example, the method of claim 18 for depositing a thin film of material on a semiconductor substrate in a processing chamber, wherein the hole in the shaft portion of the showerhead bushing has a groove shape. A method for depositing a thin film of a material on a semiconductor substrate in a processing chamber as in any of claims 1-10, wherein the secondary cleaning gas flows in a direction substantially parallel to a plane of the substrate The processing chamber. For example, a method for depositing a thin film of a material on a semiconductor substrate in a processing chamber, such as the scope of application for a patent, wherein the secondary cleaning gas flows into the processing chamber at a rate of about 1 to 30,000 sccm. An apparatus for depositing a thin film of a material on a semiconductor substrate, the apparatus includes: a processing chamber; a substrate holder located in the processing chamber; and a shower head for making a thin film precursor and a cleaning Gas flows into the processing chamber; a sprinkler sleeve is used to flow secondary cleaning gas into the processing chamber; one or more primary flow valves are used to control passage through the sprinkler head The flow rate of the film precursor and the flow rate of the primary cleaning gas; one or more secondary flow valves, which are used to control the flow of the secondary cleaning gas through the sprinkler sleeve; For removing the primary and secondary cleaning gases from the processing chamber, and for removing a thin film precursor from a surrounding volume of a substrate located in the processing chamber; a plasma generator, which is used for Generating a plasma in the processing chamber; and one or more controllers including machine-readable instructions for operating the one or more valves, the vacuum source, and the plasma generator to A thin film of material is deposited on the semiconductor substrate, Includes instructions for: (a) operating the primary flow valve to allow the film precursor to flow into the processing chamber; (b) controlling the conditions in the processing chamber such that the film precursor is adsorbed on the process An adsorption limiting layer is formed on the substrate in the chamber; (c) the primary flow valve is operated so that the primary cleaning gas flows into the processing chamber, and the valve is operated to drive a vacuum source to the primary cleaning gas Evacuating, thereby removing at least some of the unadsorbed film precursor from the surrounding volume of the adsorbed precursor; (d) operating the plasma generator to form a plasma in the processing chamber, The plasma activates the reaction of the adsorbed thin film precursor to form a thin film layer on the substrate; and (e) activates the reaction in (d) while operating the secondary flow valve to make the secondary A purge gas flows into the processing chamber, wherein the secondary purge gas includes O ₂ . For example, an apparatus for depositing a thin film of a material on a semiconductor substrate according to item 22 of the application, wherein: the showerhead includes: a rod portion; a head portion; and a hole in a bottom surface of the head portion, the The nozzle precursor is used for flowing a thin film precursor and a primary cleaning gas into the processing chamber; and the showerhead sleeve includes: a rod part; a head part; and a hole in the rod part for making secondary A purge gas flows into the processing chamber. For example, the equipment for depositing a thin film of material on a semiconductor substrate according to item 23 of the patent application, wherein the hole of the shower head is a round hole, and the hole of the shower head bushing is a slot hole.